New vat dyestuff of the anthraquinone series



Patented Feb. 14, 1933 UNITED STATES PATENT OFFICE TO GENERAL ANILINE WORKS, INC., OF NEW nmwnnn YORK, N. Y., A CORPORATION OF NEW VAT DYESTUFF OF THE ANTHRAQUINONE SERIES No Drawing. Application filed January 11, 1932, Serial No. 586,082, and in Germany January 13, 1931.

carboxylic acid of an aromatic polycyclic hydrocarbon, more particularly of a dihalide or diester of a naphthalene dicarboxylic acid, diphenyl-para-para-dicarboxylic acid or diphenylmethane dicarboxylic acid which compounds may be substituted by halogen atoms, alkylor alkoxy groups, such dicarboxylic acids being excepted as are capable of forming internal anhydrides.

In accordance with the present invention dyestuffs possessing similar good fastness properties are obtained by employing instead of the dicarboxylic acid derivatives mentioned in the above application, reactive derivatives of diphenyl dicarboxylic acids in which the 00-positions to the diphenyl linkage are joined by one or two carbon atoms to form a carbocyclic ring or by a bridge of other atoms to form a heterocyclic ring, for

example by oxygen or one or two nitrogen 0 atoms.

Such compounds are, for example, the chlorides or bromides of dicarboxylic acids of fluorene, fluorenone, diphenyloxide, carbazole and its nitrogenous allryl derivatives, phenazone.

The new dyestufis probably correspond to the formula wherein X means CH2, GO, 0, NH, N-alkyl or N N and wherein the anthraquinone nuclei may be substituted by aroylaminoor alkoxy groups, preferably benzoylaminoor methoxy groups.

They form yellow to red powders, difiicultly soluble in the usual organic solvents, dissolving in strong sulfuric acid with a yellow coloration, dyeing cotton from a brown to blue alkaline hydrosulfite vat strong yellow to bluish-red shades of good fastness properties.

The following examples illustrate the invention without, however, restricting it thereto Example 1 12 parts by weight of diphenylene-2:2'- oxide-tAJ-dicarboxylic acid dichloride (prepared by heating 4.4-di-(chloraceto) diphenylene-oxide with an alkaline hypochlorite solution of 1015 B. on the water bath, isolating the reaction product by salting out and converting the dicarboxylic acid thus formed into the corresponding dichloride by means of phosphorous pentachloride) are added to a solution heated to 60 C. of 20 parts by weight of l-amino-anthraquinone in 200 parts by weight of nitrobenzene. While stirring continually the temperature is slowly raised to 200 C. when the new dyestufi' separates in crystals. As soon as the evolution of hydrochloric acid ceases the melt is filtered and the residue is washed with benzene. For further purification the dyestufl It correis dissolved in dilute sulfuric acid. sponds probably to the formula:

E ammp Z6 2 30 parts by weight of phenazone-dicarboXylic acid dichloride M. P. 208 C. (prepared by nitrating diphenyl-LA/dicarboxylic acid reducing (for example, with zinc and ammonia) the 2.2-dinitro-diphenyl- 4L.4-dicarboxylic acid thus formed and converting the resulting dicarboxylic acid into the corresponding dichloride by means of phosphorous pentachloride), are added to a solution heated to 80100 C. of 45 parts by weight of a-amino-anthraquinone in 400 parts by weight of nitrobenzene. The mixture is stirred for half an hour at 180 C. and after cooling to 80 C. the dyestufi is filtered off with suction and washed. It corresponds probably to the formula:

It is soluble in concentrated sulfuric acid with a yellow coloration and forms a red alkaline hydrosulfite vat from which cotton is dyed a fast greenish yellow.

The product obtained with the same dicarboxylic acid dichloride and 1-amino-5 benzoylamino-anthraquinone dyes cotton from a bluish green hydrosulfite vat fast orange yellow shades.

Example 3 l he dyestuff obtainable in a similar manner as described in the foregoing example E mample 4 30 parts by weight of fluorenone-dicarboxylic acid dichloride (obtainable by condensation of fluorene with acetylchloride, OX- idation of the diacetyl compound and conversion of the dicarboxylic acid into the corresponding dichloride) are condensed with 45 parts by weight of l-amino-anthraquinone with the addition of nitrobenzene at a temperature of 180200 C. The dyestuif formed dyes cotton from a dark red vat in greenish yellow shades which possess valuable properties. It corresponds probably to the formula:

The color of the solutionin concentrated sulfuric acid is red.

On substituting the l-amino-anthraquinone by the corresponding quantity of 1- amino 5 benzoyl amino anthraquinone a dyestufi is obtained which dyes cotton from a bluish-green vat in very fast orange yellow liken ma;

wherein X means CH CO, 0, NH, N-alkyl or N=N and wherein the anthraquinone nuclei may be substituted by aroyla-minoor alkoxy groups, said dyestuffs forming yellow to red powders, nearly insoluble in the usual organic solvents, soluble in strong sulfuric acid with a yellow coloration, dyeing cotton from a brown to blue alkaline hydrosulfite vat yellow to bluish-red shades of good fastness properties.

2. The new vat dyestufl of the probable formula:

said dyestufl dyeing cotton from a dark brown vat fast yellow shades.

4:. The new vat dyestuif of the probable formula:

said dyestufi dyeing cotton from a dark red vat greenish yellow shades of a good fastness.

In testimony whereof, I afiix my signature.

ERNST H'ONOLD.

said dyestuflf dyeing cotton from a dark red vat greenish-yellow shades of a good fastness.

3. The new vat dyestufi' of the probable formula:

NH-O C O-NH 

